Method for forming capacitor of semiconductor device

ABSTRACT

Methods for forming capacitors of semiconductor devices are disclosed, and more particularly, methods for forming capacitors which comprises a contact plug, a diffusion barrier film, a lower electrode formed of ruthenium, a dielectric film formed of high dielectric constant material and an upper electrode are disclosed, wherein the diffusion barrier film having strong chemical bond, amorphous structure without rapid diffusion path of oxygen and low electrical resistance prevents diffusion of oxygen atoms during a deposition process and thermal treatment of the dielectric film to improve operation of the capacitor and reliability of the device.

BACKGROUND

[0001] 1. Technical Field

[0002] Methods for forming capacitors of semiconductor devices aredisclosed, and more particularly, methods for forming capacitors aredisclosed wherein the capacitors comprise a contact plug, a diffusionbarrier film, a lower electrode formed of ruthenium (hereinafter,referred to as ‘Ru’), a dielectric film formed of high dielectricconstant material and an upper electrode, and wherein the diffusionbarrier film prevents diffusion of oxygen atoms during a depositionprocess and thermal treatment of the dielectric film to reducedegradation of characteristics of the device.

[0003] 2. Description of the Related Art

[0004] A conventional diffusion barrier film is composed of TiN, TiAlN,TiSiN or TaSiN. A lower electrode composed of Ru or platinum is formedon the diffusion barrier film. A dielectric film is formed on the lowerelectrode using high dielectric constant materials such as BST ortantalum oxide film.

[0005] Here, the deposition process of dielectric film having highdielectric constant is carried out under oxygen atmosphere using a highthermal treatment method. As a result, oxygen atoms diffuse into thelower electrode and oxidize the diffusion barrier film.

[0006] In addition, when the lower electrode is composed of Ru film,molecular structure of Tris(2,4-octanedionato) ruthenium which is asource material must be broken down to allow the deposition of Ru film.Here, oxygen used as a reaction gas penetrates into the Ru film anddiffuses through the lower electrode during the subsequent thermalprocess, thereby oxidizing a diffusion barrier film under the lowerelectrode. The oxidized diffusion barrier film degrades electricalcharacteristics of device.

SUMMARY OF THE DISCLOSURE

[0007] Accordingly, methods for forming capacitors of semiconductordevices are disclosed wherein the capacitors comprise a diffusionbarrier film having strong chemical bond, amorphous structure withoutrapid diffusion path of oxygen and low electrical resistance in order toprevent degradation of characteristics of device during the subsequenthigh temperatures thermal process.

[0008] In order to produce the above-described capacitors one disclosedmethod comprises:

[0009] (a) forming a diffusion barrier film, wherein the diffusionbarrier film includes a RuTiN film or RuTiN/RuTiO stacked film on acontact plug for a capacitor;

[0010] (b) thermally processing the diffusion barrier film via RTP underO₂ gas atmosphere; and

[0011] (c) sequentially forming a lower electrode, a dielectric film andan upper electrode on the diffusion barrier film.

[0012] It is preferable that the RuTiN/RuTiO stacked film furthercomprises a plurality of RuTiN/RuTiO stacked films.

[0013] It is preferable that the step of thermally processing thediffusion barrier film further comprises a step of making the surface ofthe diffusion barrier film dense using ionized gas.

[0014] It is preferable that the step of forming a diffusion barrierfilm comprises a CVD process for forming the RuTiN film having athickness ranging from 200to 1000 Å performed at a temperature rangingfrom 100to 900° C.

[0015] It is preferable that the RuTiN film comprises Ti ranging from 11to 100 atom parts to 100 atom parts of Ru and N ranging from 1 to 160atom parts to 100 atom parts of Ru.

[0016] It is preferable that the RuTiN film comprises Ti ranging from 11to 67 atom parts to 100 atom parts of Ru and N ranging from 6 to 67 atomparts to 100 atom parts of Ru.

[0017] It is preferable that the step of forming a diffusion barrierfilm comprises a CVD process for forming the RuTiO film having athickness ranging from 200 to 1000 Å performed at a temperature rangingfrom 100 to 900° C.

[0018] It is preferable that the RuTiO film of RuTiN/RuTiO stacked filmcomprises Ti ranging from 11 to 100 atom parts to 100 atom parts Ru andO ranging from 1 to 100 atom parts to 100 atom parts of Ru.

[0019] It is preferable that the RuTiO film of RuTiN/RuTiO stacked filmcomprises Ti ranging from 11 to 67 atom parts to 100 atom parts of Ruand O ranging from 6 to 67 atom parts to 100 atom parts of Ru.

[0020] It is preferable that the step of forming the diffusion barrierfilm further comprises a purge process using a purge gas selected fromthe group consisting of N₂, He, Ne, Ar, H₂ and mixed gas thereof.

[0021] It is preferable that the step of forming the diffusion barrierfilm employs a Ru precursor selected from the group consisting of RuX₂and RuX₃ (where, X is selected from the group consisting of H, F, Cl,Br, I, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, C₁-C₈alkylcyclopentadienyl, cyclopentadienyl, β-diketonates, C₁-C₁₀ alkylsubstituted with halogen, C₂-C₁₀ alkenyl substituted with halogen, C₁-C₈alkoxy substituted with halogen, C₆-C₁₂ aryl substituted with halogen,C₁-C₈ alkylcyclopentadienyl substituted with halogen, cyclopentadienylsubstituted with halogen and β-diketonates substituted with halogen).

[0022] It is preferable that the Ru precursor comprisesBis(ethylcyclopentadienyl) ruthenium, Tris(2,4-octanedionato)rutheniumor Tris(6-methyl-2,4-heptanedionato) ruthenium.

[0023] It is preferable that the step of forming the diffusion barrierfilm employs a Ti precursor selected from the group consisting of TiY₄and TiY₂ (where, Y is selected from the group consisting of H, F, Cl,Br, I, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, C₁-C₈alkylcyclopentadienyl, cyclopentadienyl, β-diketonates, C₁-C₁₀ alkylsubstituted with halogen, C₂-C₁₀ alkenyl substituted with halogen, C₁-C₈alkoxy substituted with halogen, C₆-C₁₂ aryl substituted with halogen,C₁-C₈ alkylcyclopentadienyl substituted with halogen, cyclopentadienylsubstituted with halogen and β-diketonates substituted with halogen).

[0024] It is preferable that the Ti precursor comprises Titaniumtetrachloride or Titanium tetraisopropoxide.

[0025] It is preferable that the diffusion barrier film is formed usinga reaction gas selected from the group consisting of O₂, NH₃, H₂O, H₂O₂,ROH, RCOOH, C₂-C₁₀ diol and mixtures thereof (where, R is selected fromthe group consisting of H, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈ alkoxy,C₆-C₁₂ aryl, C₁-C₁₀ alkyl substituted with halogen, C₂-C₁₀ alkenylsubstituted with halogen, C₁-C₈ alkoxy substituted with halogen andC₆-C₁₂ aryl substituted with halogen).

[0026] It is preferable that the thermally processing the step (b) isperformed under a gas atmosphere selected from the group consisting ofO₂ gas, mixture gas of Ar and O₂, mixture gas of N₂ and O₂ andcombinations thereof.

[0027] It is preferable that the step of making the surface of thediffusion barrier film dense using ionized gas comprises (i) processcomprising the steps of impacting the diffusion barrier film withionized O₂, ionized Ar, ionized Ar and O₂, ionized N₂ and ionized N₂ andO₂; thermally treating the diffusion barrier film; and forming a uniformoxide layer on the surface of the diffusion barrier film using O₂ ion,(ii) process comprising the steps of thermally treating the diffusionbarrier film under NH₃ gas atmosphere, NH₃ plasma or NH₃/O₂ plasmaatmosphere; and forming a uniform oxide layer on the surface of thediffusion barrier film using O₂ ion, (iii) process comprising steps ofthermally treating the diffusion barrier film using UV—O₃ to form asurface layer or (iv) combinations thereof.

[0028] It is preferable that the thermally processing the diffusionbarrier film is performed at a temperature ranging from 100 to 650° C.for a time period ranging from 1 to 5 minutes.

[0029] It is preferable that the dielectric film is selected from thegroup consisting of a Ta₂O₅ film, a BST film, a PZT film, a SBT film, aBLT film and mixtures thereof.

[0030] A diffusion barrier film is formed that has an oxidationtolerance at high temperature under oxygen atmosphere, which preventsdegradation of characteristic of device during the subsequent thermalprocess.

[0031] A diffusion barrier film is required to prevent diffusion ofoxygen atoms and must be oxidation-resistant. In order to preventdiffusion of oxygen at high temperature, the diffusion barrier film hasan amorphous structure because the crystallization generates grainboundary, which is a rapid diffusion path of oxygen. In addition, thediffusion barrier film must have strong chemical bonding between eachconstituent to prevent oxidation and maintain conductivity afterreaction with oxygen.

[0032] Accordingly, a diffusion barrier film according to the presentinvention comprises Ru which is a quasi-precious metal, as matrix andhas oxygen or nitrogen and a small amount of Ti which is aheat-resistant metal added thereto. So that the diffusion barrier filmhas an amorphous structure due to strong chemical bonding of oxygen ornitrogen and so that the amorphous structure is maintained even at hightemperature due to Ti. Additionally, a conductive oxide film is obtainedeven after a reaction with oxygen due to Ru, thereby preventingdegradation of electrical characteristic of device.

[0033] The reaction by which a RuTiN film and RuTiO film is formed asfollows.

[0034] A RuTiN film is formed on a substrate heated at a temperatureranging from 100 to 900° C. using RuX₂ as Ru precursor, TiY₄ as Tiprecursor and NH₃ as reaction gas, according to the first and the secondreaction formulas:

RuX₂———(NH₃)→Ru+2HX(↑)  first formula

TiY₄———(NH₃)→TiN+2HY(↑)  second formula.

[0035] The reaction gas NH₃ reacts with Ru precursor and Ti precursoraccording to the above reaction formulas to form Ru and TiN. As aresult, a RuTiN film wherein Ru and TiN are irregularly deposited isformed. Here, HX and HY, which is strong volatile reaction products, areeasily removed via a vacuum.

[0036] A RuTiO film is formed on a substrate heated at a temperatureranging from 100 to 900° C. using RuX₂ as Ru precursor, TiY₄ as Tiprecursor and O₂ as reaction gas, according to the third and the fourthreaction formulas:

RuX₂———(O₂)→RuO_(x)+2XO₂(↑)  third formula

TiY₄———(O₂)→TiO_(x)+4YO₂(↑)  fourth formula

[0037] The reaction gas O₂ reacts with Ru precursor and Ti precursoraccording to the above reaction formulas to form RuO_(x) and TiO_(x). Asa result, a RuTiO film wherein RuO_(x) and TiO_(x) are irregularlydeposited is formed. Here, XO₂ and YO₂, which is strong volatilereaction products, are easily removed via a vacuum.

[0038] However, a RuTiN film and a RuTiO film may also be formed usingother Ru precursor and Ti precursor.

[0039] A RuTiN film is formed on a substrate heated at a temperatureranging from 100 to 900° C. using RuX₃ as Ru precursor, TiY₄ as Tiprecursor and NH₃as reaction gas, according to the fifth and the sixthreaction formulas:

RuX₃———(NH₃)→Ru+3HX(↑)  fifth formula

TiY₄———(NH₃)→TiN+HY(↑)  sixth formula

[0040] The reaction gas NH₃reacts with Ru precursor and Ti precursoraccording to the above reaction formulas to form Ru and TiN. As aresult, a RuTiN film wherein Ru and TiN are irregularly deposited isformed. Here, HX and HY, which is strong volatile reaction products, areeasily removed via a vacuum.

[0041] A RuTiO film is formed on a substrate heated at a temperatureranging from 100 to 900° C. using RuX₃ as Ru precusor, TiY₄ as Tiprecursor and O₂ as reaction gas, according to the seventh and theeighth reaction formulas:

RuX₃———(O₂)→RuO_(x)+3XO₂(↑)  seventh formula

TiY₂———(O₂)→TiO_(x)+2YO₂(↑)  eighth formula

[0042] The reaction gas O₂ reacts with Ru precursor and Ti precursoraccording to the above reaction formulas to form RuO_(x) and TiO_(x). Asa result, a RuTiO film wherein RuO_(x) and TiO_(x) are irregularlydeposited is formed. Here, XO₂ and YO₂, which is strong volatilereaction products, are easily removed via a vacuum.

[0043] Here, the diffusion barrier film may be a RuTiN film, aRuTiN/RuTiO stacked film or a stacked structure of a plurality ofRuTiN/RuTiO stacked films.

BRIEF DESCRIPTION OF THE DRAWINGS

[0044]FIGS. 1a to 1 d are cross-sectional diagrams illustrating a methodfor forming a capacitor of a semiconductor device in accordance with apreferred embodiment.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

[0045] A method for forming a capacitor of a semiconductor device willbe described in greater detail while referring to the accompanyingdrawings.

[0046]FIGS. 1a to 1 d are cross-sectional diagrams illustrating a methodfor forming a capacitor of a semiconductor device in accordance with apreferred embodiment. The diagrams illustrates a diffusion barrier filmformed on a polysilicon contact plug, and a capacitor comprising a lowerelectrode, a dielectric film and an upper electrode sequentially formedon the diffusion barrier film.

[0047] Referring to FIG. 1a, a diffusion barrier film 13 is formed on acontact plug 11. Here, the diffusion barrier film 13 comprises a RuTiNfilm, RuTiN/RuTiO stacked film or a stacked structure of a plurality ofRuTiN/RuTiO stacked films. After formation of the diffusion barrier film13, it is preferable that the surface thereof be made dense or impactedby oxygen.

[0048] The RuTiN film which is the diffusion barrier film 13 preferablyhas a thickness ranging from 200 to 1000 Å and is formed using a CVDmethod at a temperature ranging from 100 to 900° C. The RuTiN filmcomprises Ti ranging from 11 to 100 atom parts to 100 atom parts of Ruand N ranging from 1 to 160 atom parts to 100 atom parts of Ru,preferably Ti ranging from 11 to 67 atom parts to 100 atom parts of Ruand N ranging from 6 to 67 atom parts to 100 atom parts of Ru.

[0049] Specifically, the RuTiN film is formed on a substrate heated at atemperature ranging from 100 to 900° C. using RuX₂ as Ru precursor, TiY₄as Ti precursor and NH₃as reaction gas, according to the above-describedfirst and the second reaction formulas.

[0050] The reaction gas NH₃ reacts with Ru precursor and Ti precursor toform Ru and TiN and the RuTiN film wherein Ru and TiN are irregularlydeposited is formed. Here, HX and HY, which is strong volatile reactionproducts, are easily removed via vacuum.

[0051] The RuTiO film which is the diffusion barrier film 13 preferablyhas a thickness ranging from 200 to 1000 Å and is formed using a CVDmethod at a temperature ranging from 100 to 900° C. The RuTiO film ofRuTiN/RuTiO stacked film comprises Ti ranging from 11 to 100 atom partsto 100 atom parts Ru and O ranging from 1 to 100 atom parts to 100 atomparts of Ru, preferably Ti ranging from 11 to 67 atom parts to 100 atomparts of Ru and O ranging from 6 to 67 atom parts to 100 atom parts ofRu.

[0052] Specifically, the RuTiO film is formed on a substrate heated at atemperature ranging from 100 to 900° C. using RuX₂ as Ru precursor, TiY₄as Ti precursor and O₂ as reaction gas, according to the third and thefourth reaction formulas.

[0053] The reaction gas O₂ reacts with Ru precursor and Ti precursor toform RuO_(x)and TiO_(x) and the RuTiO film wherein RuO_(x) and TiO_(x)are irregularly deposited is formed. Here, XO₂ and YO₂, which is strongvolatile reaction products, are easily removed via vacuum.

[0054] For RuX₂ which is a Ru precursor, X is selected from the groupconsisting of H, F, Cl, Br, I, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈alkoxy, C₆-C₁₂ aryl, C₁-C₈ alkylcyclopentadienyl, cyclopentadienyl,β-diketonates, C₁-C₁₀ alkyl substituted with halogen, C₂-C₁₀ alkenylsubstituted with halogen, C₁-C₈ alkoxy substituted with halogen, C₆-C₁₂aryl substituted with halogen, C₁-C₈ alkylcyclopentadienyl substitutedwith halogen, cyclopentadienyl substituted with halogen andβ-diketonates substituted with halogen. Specifically,Bis(ethylcyclopentadienyl)ruthenium, Tris(2,4-octanedionato)ruthenium orTris(6-methyl-2,4-heptanedionato)ruthenium is used for the Ru precursor.

[0055] For TiY₄ which is a Ti precursor, Y is selected from the groupconsisting of H, F, Cl, Br, I, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈alkoxy, C₆-C₁₂ aryl, C₁-C₈ alkylcyclopentadienyl, cyclopentadienyl,β-diketonates, C₁-C₁₀ alkyl substituted with halogen, C₂-C₁₀ alkenylsubstituted with halogen, C₁-C₈ alkoxy substituted with halogen, C₆-C₁₂aryl substituted with halogen, C₁-C₈ alkylcyclopentadienyl substitutedwith halogen, cyclopentadienyl substituted with halogen andβ-diketonates substituted with halogen. Specifically, Titaniumtetrachloride or Titanium tetraisopropoxide is used for the Tiprecursor.

[0056] Preferably, the reaction gas used during the deposition processof the diffusion barrier film 13 is selected from the group consistingof H₂O, H₂O₂, ROH, RCOOH, C₂-C₁₀ diol or mixtures thereof instead of theabove-described O₂ and NH₃.

[0057] Preferably, the R is selected from the group consisting of H,C_(1-C) ₁₀ alkyl, C₂C₁₀ alkenyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, C₁-C₁₀ alkylsubstituted with halogen, C₂-C₁₀ alkenyl substituted with halogen, C₁-C₈alkoxy substituted with halogen, C₆-C₁₂ aryl substituted with halogen.

[0058] The deposition process of the diffusion barrier film 13 isaccompanied by a purge process using a purge gas selected from the groupconsisting of N₂, He, Ne, Ar, H₂ or mixtures thereof.

[0059] A method for making the surface of the RuTiN film or the RuTiOfilm dense or impacted by oxygen is described as follows.

[0060] First, a method for impacting the surface of the RuTiN film orthe RuTiO film with oxygen includes:

[0061] a) thermally processing a RuTiN film or RuTiO film via RTP at atemperature ranging from 100 to 650° C. under O₂ atmosphere for a timeperiod ranging from 1 to 5 minutes;

[0062] b) thermally processing a RuTiN film or RuTiO film via RTP at atemperature ranging from 100 to 650° C. under mixed gas atmosphere of Arand O₂ for a time period ranging from 1 to 5 minutes with the amount ofAr and O₂ being varied;

[0063] c) thermally processing a RuTiN film or RuTiO film via RTP at atemperature ranging from 100 to 650° C. under mixed gas atmosphere N₂and O₂ for a period of time ranging from 1 to 5 minutes with the amountof N₂ and O₂ being varied; and

[0064] d) combinations thereof.

[0065] Additionally, methods for making the surface of the RuTiN film orRuTiO film dense and impacted by oxygen comprise:

[0066] a) impacting a RuTiN film or a RuTiO film with ionized O₂ to makethe films dense, thermally processing the films at a temperature rangingfrom 100 to 650° C. for 1 to 5 minutes and then forming a uniform oxidelayer using O₂ ion;

[0067] b) impacting a RuTiN film or a RuTiO film with ionized Ar to makethe films dense, thermally processing the films at a temperature rangingfrom 100 to 650° C. for a time period ranging from 1 to 5 minutes andthen forming a uniform oxide layer using O₂ ion;

[0068] c) impacting a RuTiN film or a RuTiO film with ionized Ar and O₂to make the films dense, thermally processing the films at a temperatureranging from 100 to 650° C. for a time period ranging from 1 to 5minutes and then forming a uniform oxide layer using O₂ ion;

[0069] d) impacting a RuTiN film or a RuTiO film with ionized N₂ to makethe films dense, thermally processing the films at a temperature rangingfrom 100 to 650° C. for a time period ranging from 1 to 5 minutes andthen forming a uniform oxide layer using O₂ ion;

[0070] e) impacting a RuTiN film or a RuTiO film with ionized N₂ and O₂to make the films dense, thermally processing the films at a temperatureranging from 100 to 650° C. for a time period ranging from 1 to 5minutes and then forming a uniform oxide layer using O₂ ion;

[0071] f) thermally processing a RuTiN film or a RuTiO film at atemperature ranging from 100 to 650° C. under NH₃ gas atmosphere for atime period ranging from 1 to 5 minutes and then forming a uniform oxidelayer using O₂ ion;

[0072] g) thermally processing a RuTiN film or a RuTiO film at atemperature ranging from 100 to 650° C. under NH₃plasma atmosphere for atime period ranging from 1 to 5 minutes and then forming a uniform oxidelayer using O₂ ion;

[0073] h) thermally processing a RuTiN film or a RuTiO film at atemperature ranging from 100 to 650° C. under NH₃/O₂ plasma atmospherefor a time period ranging from 1 to 5 minutes and then forming a uniformoxide layer using O₂ ion;

[0074] i) thermally processing a RuTiN film or a RuTiO film at atemperature ranging from 100 to 650° C. for a time period ranging from 1to 5 minutes using UV—O₃; and

[0075] j) combinations thereof.

[0076] Referring to FIG. 1b, a lower electrode 15 is formed bydepositing a Ru film on the diffusion barrier film 13.

[0077] Referring to FIG. 1c, a dielectric film 17 having high dielectricconstant is formed on the lower electrode 15. Here, the dielectric film17 is selected from the group consisting of a Ta₂O₅ film, a BST film, aPZT film, a SBT film, a BLT film and mixtures thereof.

[0078] Referring to FIG. 1d, an upper electrode 19 is formed on thedielectric film 17 by depositing a TiN film or a Ru film.

[0079] In another preferred embodiment of the present invention, theRuTiN film is formed on a substrate heated at a temperature ranging from100 to 900° C. using RuX₃ as Ru precursor, TiY₄ as Ti precursor and NH₃as reaction gas, according to the fifth and the sixth reaction formulas.

[0080] The reaction gas NH₃ reacts with Ru precursor and Ti precursor toform Ru and TiN and the RuTiN film wherein Ru and TiN are irregularlydeposited is formed. Here, HX and HY, which is strong volatile reactionproducts, are easily removed via vacuum.

[0081] For RuX₃ which is a Ru precursor, X is as described above.

[0082] Additionally, the RuTiO film is formed on a substrate heated at atemperature ranging from 100 to 900° C. using RuX₃ as Ru precusor, TiY₄as Ti precursor and O₂ as reaction gas, according to the seventh and theeighth reaction formulas.

[0083] The reaction gas O₂ reacts with Ru precursor and Ti precursor toform RuO_(x) and TiO_(x) and the RuTiO film wherein RuO_(x) and TiO_(x)are irregularly deposited is formed. Here, XO₂ and YO₂, which is strongvolatile reaction products, are easily removed via vacuum.

[0084] For TiY₂ which is a Ti precursor, Y is as described above.

[0085] As discussed earlier, in the disclosed methods, diffusion ofoxygen is effectively prevented during the deposition process andthermal process of a dielectric film having high dielectric constant,thereby preventing degradation of characteristic of device and improvingcharacteristics of DRAM and FeRAM for high integration of the producedsemiconductor devices.

What is claimed is:
 1. A method for forming a capacitor of asemiconductor device comprising: (a) forming a diffusion barrier film,wherein the diffusion barrier film includes a RuTiN film or RuTiN/RuTiOstacked film on a contact plug for a capacitor; (b) thermally processingthe diffusion barrier film via RTP under O₂ gas atmosphere; and (c)sequentially forming a lower electrode, a dielectric film and an upperelectrode on the diffusion barrier film.
 2. The method according toclaim 1, wherein the RuTiN/RuTiO stacked film further comprises aplurality of RuTiN/RuTiO stacked films.
 3. The method according to claim1, wherein the step of thermally processing the diffusion barrier filmfurther comprises a step of making the surface of the diffusion barrierfilm dense using ionized gas.
 4. The method according to claim 1,wherein the step of forming a diffusion barrier film comprises a CVDprocess for forming the RuTiN film having a thickness ranging from 200to 1000 Å performed at a temperature ranging from 100 to 900° C.
 5. Themethod according to claim 1, wherein the RuTiN film comprises Ti rangingfrom 11 to 100 atom parts to 100 atom parts of Ru and N ranging from 1to 160 atom parts to 100 atom parts of Ru.
 6. The method according toclaim 5, wherein the RuTiN film comprises Ti ranging from 11 to 67 atomparts to 100 atom parts of Ru and N ranging from 6 to 67 atom parts to100 atom parts of Ru.
 7. The method according to claim 1, wherein thestep of forming a diffusion barrier film comprises a CVD process forforming the RuTiO film having a thickness ranging from 200 to 1000 Åperformed at a temperature ranging from 100 to 900° C.
 8. The methodaccording to claim 1, wherein the RuTiO film of RuTiN/RuTiO stacked filmcomprises Ti ranging from 11 to 100 atom parts to 100 atom parts Ru andO ranging from 1 to 100 atom parts to 100 atom parts of Ru.
 9. Themethod according to claim 8, wherein the RuTiO film of RuTiN/RuTiOstacked film comprises Ti ranging from 11 to 67 atom parts to 100 atomparts of Ru and O ranging from 6 to 67 atom parts to 100 atom parts ofRu.
 10. The method according to claim 1, wherein the step of forming thediffusion barrier film further comprises a purge process using a purgegas selected from the group consisting of N₂, He, Ne, Ar, H₂ and mixedgas thereof.
 11. The method according to claim 1, wherein the step offorming the diffusion barrier film employs a Ru precursor selected fromthe group consisting of RuX₂ and RuX₃ (where, X is selected from thegroup consisting of H, F, Cl, Br, I, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈alkoxy, C₆-C₁₂ aryl, C₁-C₈ alkylcyclopentadienyl, cyclopentadienyl,β-diketonates, C₁-C₁₀ alkyl substituted with halogen, C₂-C₁₀ alkenylsubstituted with halogen, C₁-C₈ alkoxy substituted with halogen, C₆-C₁₂aryl substituted with halogen, C₁-C₈ alkylcyclopentadienyl substitutedwith halogen, cyclopentadienyl substituted with halogen andβ-diketonates substituted with halogen).
 12. The method according toclaim 11, wherein the Ru precursor comprisesBis(ethylcyclopentadienyl)ruthenium, Tris(2,4-octanedionato)ruthenium orTris(6-methyl-2,4-heptanedionato)ruthenium.
 13. The method according toclaim 1, wherein the step of forming the diffusion barrier film employsa Ti precursor selected from the group consisting of TiY₄ and TiY₂(where, Y is selected from the group consisting of H, F, Cl, Br, I,C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, C₁-C₈alkylcyclopentadienyl, cyclopentadienyl, β-diketonates, C₁-C₁₀ alkylsubstituted with halogen, C₂-C₁₀ alkenyl substituted with halogen, C₁-C₈alkoxy substituted with halogen, C₆-C₁₂ aryl substituted with halogen,C₁-C₈ alkylcyclopentadienyl substituted with halogen, cyclopentadienylsubstituted with halogen and β-diketonates substituted with halogen).14. The method according to claim 11, wherein the Ti precursor comprisesTitanium tetrachloride or Titanium tetraisopropoxide.
 15. The methodaccording to claim 1, wherein the step of forming the diffusion barrierfilm employs a reaction gas selected from the group consisting of O₂,NH₃, H₂O, H₂O₂, ROH, RCOOH, C₂-C₁₀ diol and mixed gas thereof (where, Ris selected from the group consisting of H, C₁-C₁₀ alkyl, C₂-C₁₀alkenyl, C₁-C₈ alkoxy, C₆-C₁₂ aryl, C₁-C₁₀ alkyl substituted withhalogen, C₂-C₁₀ alkenyl substituted with halogen, C₁-C₈ alkoxysubstituted with halogen and C₆-C₁₂ aryl substituted with halogen). 16.The method according to claim 1, wherein the step (b) is performed undera gas atmosphere selected from the group consisting of O₂ gas, mixturegas of Ar and O₂, mixture gas of N₂ and O₂ and combinations thereof. 17.The method according to claim 3, wherein the step of making the surfaceof the diffusion barrier film dense using ionized gas comprises (i)process comprising the steps of impacting the diffusion barrier filmwith ionized O₂, ionized Ar, ionized Ar and O₂, ionized N₂ and ionizedN₂ and O₂; thermally treating the diffusion barrier film; and forming auniform oxide layer on the surface of the diffusion barrier film usingO₂ ion, (ii) process comprising the steps of thermally treating thediffusion barrier film under NH₃ gas atmosphere, NH₃ plasma or NH₃/O₂plasma atmosphere; and forming a uniform oxide layer on the surface ofthe diffusion barrier film using O₂ ion, (iii) process comprising stepsof thermally treating the diffusion barrier film using UV—O₃ to form asurface layer or (iv) combinations thereof.
 18. The method according toany one of claims 16 and 17, wherein the thermally processing thediffusion barrier film is performed at a temperature ranging from 100 to650° C. for a time period ranging from 1 to 5 minutes.
 19. The methodaccording to claim 1, wherein the dielectric film is selected from thegroup consisting of a Ta₂O₅ film, a BST film, a PZT film, a SBT film, aBLT film and combinations thereof.